Method of modifying oxyalkylated phenol-aldehyde resins with polyepoxide resins and product resulting therefrom



United States Patent Cilice Patented Dec. 16, 1958 METHOD OF MODWYING OXYALKYLATED PHENOL-ALDEHYDE RESINS WITH'POLYEPOX- IDE RESINS ANE) PRODUCT RESULTING THEREFROM Melvin De Groote, St. Louis, and Kwan-Ting Sheri, Brentwood, Mm, assignors to Petrolite Corporation, Wilmington, Del., a corporation of Delaware No Drawing. Original application November 19, 1953, Serial No. 393,224, now Patent No. 2,792,357, dated May 14, 1957; Dividedand thisapplication January 22, 1957, Serial No. 635,152

3 Claims. (Cl. 260-43) The present application is a continuation-in-part of our co-pending applications, Serial No. 343,804, filed March 20, 1953, now abandoned, and Serial No. 349,972, filed April 20, 1953, now U. .8. Patent No. 2,792,353, dated May 14, .1957, and a division of our copending application Serial No. 393,224, filed November 19, 1953, now U. S. Patent No. 2,792,357, dated May 14, 1957. The first of said copending applications relates to a process for breaking petroleum emulsions of the water-in-oil type employing a demulsifier including the reaction products of (A) certain oxyalkylated phenolaldehyde resins, therein. described in detail, and (B) certain phenolic polyepoxides and cogenerically associated compounds formed in their preparation, also therein described in detail, the ratio of reactant (A) to reactant (B) being in the proportion of 2 moles of (A) to one mole of.(B).

The second of the aforementioned co-pending applications is comparable to the above application, Serial No. 343,804, except that the polyepoxide employed is a non-aryl hydrophile polyepoxide which is therein described in detail.

Note that in both patent applications the molal ratio of oxyalkylated resin to polyepoxide is 2 to 1.

In our 2 co-pending applications, Serial Nos. 393,221, now U. S. Patent No. 2,819,212, dated January 7, 1958, and 393,223, now U. S. Patent No. 2,792,356, dated May 14, 1957, the same situation applies except that the molar ratio is 4 to 3 instead of 2 to 1. Co-pending application, Serial No. 393,221 employs the same type of polyepoxide as in Serial No. 343,804. Likewise, co-

pending application, Serial No. 393,223 employs the same type of epoxide as co-pendingapplication, Serial No. 349,972.

In the present application the molal ratio again is 4 to 3 and not 2 to 1 and involves both types of polyepoxides. Stated another way, the hydrophile polyepoxide described in Serial No. 349,972 is employed first in a 2 to 1 ratio, and then 2 moles of this larger molecule are united by one mole of the hydrophobe polyepoxide described in Serial No. 343,804. Thus, it is obvious that the present application employs the products described in Serial No. 349,972 as an intermediate. For this reason much of the text is identical with that found in Serial No. 349,972, but that part of the text which describes the hydrophile polyepoxide in Serial No. 343,804 also appears in the present description.

Thus the present invention relates to new chemical products or-compounds useful as demulsifying agents in processes or procedures particularly adapted for preventing, breaking or resolving emulsions of the water-inoil type and particularly petroleum emulsions. The new products are the reaction products of (A) certain oxyalkylated phenol-aldehyde resins, hereinafter described in detail, and (B) certain non-aryl hydrophile polyepoxides, hereinafter described in detail, further reacted with (C) certain phenolic polyepoxides and cogenerically associated compounds formed in their preparation, also hereinafter described in detail. The reactants (A) and (B) are reacted in the molar proportion of- 2:1 respecof the intermediate (A-B-A) can be combined with one mole ofa hydrophile polyepoxide and particularly a hydrophile diepoxide, thus:

Not only--is the present application concerned with the above described-materials which serve for the purpese' of resolvi'n'g petroleum emulsions but also with the products as-'suchand the method of producing the same. Thus, the products just described for use in the resolutionof petroleum emulsions of the water-in-oil type and obtained in the manner set forth, are useful for a variety of purposes.

The products previously described which are obtained by reaction between a polyepoxide and certain oxyalkylation derivatives are useful for various purposes includingthe resolution of petroleum emulsions-of the Water-inoil type, are obtained from certain heat-stable resins, which, since they are heat-stable, are also susceptible to reaction in various ways to yield products other than oxyalkylation products, such as'amine derivatives. Such amine derivatives may be obtained, for example, by sub jecting the resins to reaction with ethylene imine, propylene imine, or similar imines rather than reaction with ethylene oxide, propylene oxide, etc. Comparable compounds are obtained by derivatives which, in addition to having the imine radical, have an ether linkage such as H wherein R is a comparatively small alkyl radical, such as methyl, ethyl, propyl, etc. In light of this fact, i. e.,

that the reaction productsof the selected resins herein described and the epoxides are apparently new per se' and may be utilized in a manner other than specifically described herein, it is obvious they represent part of the instant invention. The resultants obtained by reaction between the resinous materials and the imine type reactant exemplify new compounds having propertiesusually found in cationic surface-active agents and can be used for the purposes for which these materials are commonly employed. The materials so obtained are still susceptible to oxyalkylation with an alkylene oxide, such as ethyleneoxide, propylene oxide, etc., and can hereacted with these oxides in the samemanner as herein. described in connection with the resinous materials which have not been subjected to the with an imine.

Actually anyreference in the claims or specification to intermediate reaction the property of being oxyalkylation-susceptible might just as properly be characterized as being imine-reactive or for that matter as oxyalkylation-susceptible and imine-reactive.

The products obtained by reaction between the oxyalkylate'd derivatives and the polyepoxides are obviously acylation-susceptible as well as being oxyalkylation-susceptible. For instance, theycould be subjected to reaction with alkylene oxides different than those previously describechas for example, styrene oxide. These derivatives additionally must have a number of aliphatic hydroxyl groups. Such aliphatic hydroxyl groups as differentiated from phenolichydroxyl groups present in one of the initial reactants are particularly susceptible to acylation with various carboxylic and non-carboxylic acids. They may be reacted with detergent-forming monocarboxy acids, particularly higher fatty acids, which are saturated or unsaturated, as well as polycarboxy acids, such as phthalic anhydride, maleic anhydride, etc. Similarly, they can be reacted with maleic acid or a fractional maleic acid ester, such as the mono-octyl ester of maleic acid, and the neutral ester obtained can be reacted with sodium bisulfite so as to introduce a sulfonic group.

As has been pointed out in our aforementioned copending application, Serial Number 337,884, filed February 19, 1953, there are two types of polyepoxides, particularly diepoxides, one being, for example characterized by the formula:

wherein R represents the divalent hydrocarbon radical of a dihydric phenol and n is an integer of the series 0, 1, 2, 3, etc. More specifically, such diglycidyl ethers may be illustrated by the following formula:

011a I CHzCHCH: O E O-GHzCHOHCHn H:

wherein n is an integer of the series 0, 1, 2, 3, etc.

In contradistinction to such diglycidyl ethers which introduce an essentially hydrophobe radical or radicals, the present invention is characterized by analogous compounds derived from diglycidyl ethers which do not introduce any hydrophobe properties in its usual meaning but in fact are more apt to introduce hydrophile properties.

Thus, in the instant invention the initial use of a polyepoxide and particularly a diglycidyl ether involves the use of one which introduces hydrophile character. Thus, the first stage involves a hydrophile polyepoxide. Stated another way, the intermediate is the result of a reaction involving such hydrophile epoxide. Thus, the diepoxides employed in the present invention as firststage reactants are characterized by the fact that the divalent radical connecting the terminal epoxide radicals contains less than carbon atoms in an interrupted chain. For instance, a simple member and one of the most readily available members of the class of diepoxides described in our co-pending application, Serial No. 324,814, filed December 8, 1952, now abandoned, is

radicals are separated by the divalent hydrophobe group The diepoxides employed as first-stage reactants in the present process are obtained from glycols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butylene glycol, dibutylene glycol, tributylene glycol, glycerol, diglycerol, triglycerol, and similar compounds. Such products are well known and are characterized by the fact that there are not more than 4 uninterrupted carbon atoms in any group which is part of the radical joining the epoxide groups. Of necessity such diepoxides must be non-aryl or aliphatic in character. The diglycidyl ethers of our co-pending application, Serial No. 324,814, filed December 8, 1952, are invariably and inevitably aryl in character.

The diepoxides employed as first-stake reactants in the present process are usually obtained by reacting a glycol or equivalent compound, such as glycerol or diglycerol with epichlorohydrin and subsequently with an alkali. Such diepoxides have been described in the literature and particularly the patent literature. See, for example,

4 Italian Patent 400,973, dated August 8, 1951; see, also, British Patent 518,057, dated December 10, 1938; and U. S. Patent No. 2,070,990, dated February 16, 1937 to Groll et al. Reference is made also to U. S. Patent No.

5 2,581,464, dated January 8, 1952, to Zech. This particular last mentioned patent describes a composition of the following general formula:

in which at is at least 1, z varies from less than 1 to more than 1, and x and z together are at least 2 and not more than 6, and R is the residue of the polyhydric alcohol remaining after replacement of at least 2 of the o O('3H2CHOCHz CHz Reference to being thermoplastic characterizes them as being liquids at ordinary temperature or readily convertible to liquids by merely heating below the point of pyrolysis and thus differentiates them from infusible resins. Reference to being soluble in an organic solvent means any of the usual organic solvents such as alcohols, ketones, esters, ethers, mixed solvents, etc. Reference to solubility is merely to differentiate from a reactant which is not soluble and might be not only insoluble but also infusible. Furthermore, solubility is a factor insofar that it is sometimes desirable to dilute the compound containing the epoxy rings before reacting with a resin as described. In such instances, of course, the solvent selected would have to be one which is not susceptible to oxyalkylation, as for example, kerosene, benzene, toluene dioxane, various ketones, chlorinated solvents, dibutyl ether, dihexyl ether, ethyleneglycol diethylether, diethyleneglycol diethylether, and dimethoxytetraethyleneglycol.

The expression epoxy is not usually limited to the 1,2-epoxy ring. The 1,2-epoxy ring is sometimes referred to as the oxirane ring to distinguish it from other epoxy rings. Hereinafter the word epoxy unless indicated otherwise, will be used to mean the oxirane ring i. e., the 1,2-epoxy ring. Furthermore, where a compound has 70 two or more oxirane rings they will be referred to as polyepoxides. They usually represent, of course, 1,2- epoxide rings or oxirane rings in the alpha-omega position. This is a departure, of course, from the standpoint of a strictly formal nomenclature as in the example of the simplest diepoxide which contains at least 4 carbon 5. atoms and is formally described .as 1.,-2.-.epoxy-.3 .4-epox-ybutane (-1,2,3,4 diepoxybutane).

.It well may be-that even though the'previouslysuggested formula represents the principal component, or components, of the resultant or reaction product described in the previous text, it may be important to note that somewhat similar compounds, generally of much higher molecular weight, have been described as complex resinous epoxides which are polyether derivatives of polyhydric phenolscontaining fan-average of more than one epoxide group per molecule and free from functional groups other than epoxide and hydroxyl groups. See U. S. Patent No. 2,494,295, dated January 10, 1950, to Greenlee. The compounds hereIincluded-are limited to the monomers or the low molal members of such series and generally contain two epoxide rings per molecule and may be entirely free from a 'hydroxyl group. This is important because theinstant :invention is directed toward products which are not insoluble resins and have certain solubility characteristics .-.not inherent in the usual thermosetting resins. Note, for example, that said U. S. Patent No. 2,494,295 describes products wherein the epoxide derivativecan combine with a sulfonamide resin. The intention in said U. 8. Patent 2,494,295, of course, is to obtain ultimately a suitable resinous product having the characteristics of a comparativelyinsoluble resin. Simply for purpose of illustration to show atypical diglycidyl etherof the kind herein employed, reference is made to the following formula:

or if derived from cyclic diglycerol-the structure'would be thus:

or the equivalent compound wherein the ring structure involves only six atoms thus:

Commercially available compounds seem to be largely to the former with comparatively small amounts, in fact comparatively minor amounts, of the latter.

Having obtained a reactant having generally 2 epoxy rings as depicted in the nextto last formula preceding, or low molal polymers thereof, it'becomes obvious the reaction'can take place with any oxyalkylated phenol-aldehyde resin by virtue of the fact that there are always present either phenolic 'hydroxyls or'their alkanol radicals or the equivalent or alkanol radicals in the presence of any phenolic hydroxyl. Indeed, the products obtained by oxyalkylation of the phenolic resins must invariably and inevitably be oXyalkylation-susceptible.

To illustratev the products which represent thesubject matter of the. present-invention, reference will .be made to a reaction involving a mole of. the oxyalkylating agent, i. e., the compound having two. oxirane rings-and an oxyalkylated resin. Proceeding with the example previously described, it is.cbvious the reaction ratio of two moles of the oxyalkylated resin. to one mole of, the

a oxyalkylating agent gives .a product-whichimay .ibeii n- .dicated as follows:

in which n is a small whole number less than 10, and usually less than 4, and including O,-and -R represents a divalent radical as previously described being-freefrom any radical .having more than'4 uninterrupted carbon atoms in a single chain, andsthe characterization oxylkylated resin is simply an abbreviation for the oxyalkylated resin which'is described in -greate'r detail esubsequently.

:Such products must be soluble in suitable solvents such asa non-oxygenated hydrocarbon .solventnor-ran oxygenated hydrocarbon solvent or, "for zthat matte r,,--a mixtureof the same with water. Needless to;s,ay,-after the resin has been treated with a large amount of ethylene oxide, the products are water soluble and maybe soluble in an acid solution.

The purpose 'inthis instance is to differentiate from insoluble resinous materials, particularly. those resultingfrom gelation or cross-linking. ,Notonly does this property serve to differentiate,from instances wherean insoluble material is desired, but also serves to emphasize the fact that in many instances the preferred compounds have distinct water-solubility or are distinctly soluble in 5% acetic acid. For instance, the products freed from any solvent can be shakenwith five to twenty times their weight of distilled water at ordinary temperature and are at least self-dispersing, and in many instances watersoluble, in fact, colloidally soluble.

Basic nitrogen atoms can be;introduce d into such derivatives by use of areactant having botha nitrogen group .and a .1,2-.epoxy. group, such as :3-diallgylaminoepoxypropane. .See .U. S.-Patent No. 2,520,093, dated August 22, 1950, to Gross.

For purpose of convenience what isysaid hereinafter will be divided into ten parts, with Part 7, in turn, being divided into three subdivisions.

Part 1 is concerned with the hydrophile type of polyepoxide and particularly the hydrophile type .of 541iepoxidereactant, i. e., the one thatenters intothe formation of the intermediate ABA.

Part 2 is concerned with suitable phenol-aldehyde resins to be employed for reaction with the epoxides.

Part 3 is concerned with the oxyalkylation of the previously described phenol-aldehyde resins.

Part 4 is concerned with the procedure involving the preparation of an intermediate byreactionbetweenstwo moles of the oxyalkylated phenol aldjehyde resin "and one mole of the diglycidyl ether, for example (identical with the products described in aforementioned co-pending application, Serial No. 349,972) followed by a second step in which 2 moles of these larger molecules are combined with a single mole ,of. the diglycidyl. ether'or thealike. Thisintermediate has been described previously as =ABA.

'Part 5 is concerned with our preference in regard to phenolic reactants suitable for the preparationof hydro phobe diepoxides.

PART 1 Reference is made to previous patents as illustrated in the manufacture of the non-aryl polyepoxides and particularly diepoxides employed as reactants in the instant invention. More specifically, such patents are the following: Italian Patent No. 400,973, dated August 8, 1941; British Patent No. 518,057, dated December 10, 1938; U. S. Patent No. 2,070,990, dated February 16, 1937, to Groll et al.; and U. S. Patent No. 2,581,464, dated January 8, 1952, to Zech. The simplest diepoxide is probably the one derived from 1,3-butadiene or isoprene. Such derivatives are obtained by the use of peroxides or by othersuitable means and the diglycidyl ethers may be indicated thus:

In some instances the compounds are essentially derivatives of etherized epichlorohydrin or methyl epichlorohydrin. Needless to say, such compounds can be derived from glycerol monochlorohydrin by etherization prior to ring closure. An example is illustrated in the previously mentioned Italian Patent No. 400,973:

Another type of diepoxide is diisobutenyl dioxide as described in aforementioned U. S. Patent No. 2,070,990, dated February 16, 1937, to Groll, and is of the following formula:

on; on,

The diepoxides previously described may be indicated in which R' represents a hydrogen atom or methyl radical and R representsthe divalent radical uniting the two terminal epoxide groups, and n is the numeral or 1. As previously pointed out, in the case of the butadiene derivative, n is 0. In the case of diisobutenyl dioxide R" is CH CH and n is 1. In another example previously referred to R'" is CH OCH and n is 1.

However, for practical purposes the onlydiepoxide available in quantities other than laboratory quantities is a derivative of glycerol or epichlorohydrin. This particular dicpoxide is obtained from diglycerol which is largely acyclic diglycerol, and epichlorohydrin or equivalent thereof, in that the epichlorohydrin itself may supply the glycerol or diglycerol radical in addition to the epoxy rings. As has been suggested previously, instead of starting with glycerol or a glycerol derivative, one could start with any one of a number of glycols or polyglycols 8 and 'it is more convenient to include as part of the terminal oxirane ring radical the oxygen atom that was derived from epichlorohydrin or, as might be the case, methyl epichlorohydrin. So presented the formula becomes:

In the above formula R is selected from groups such as the following:

It is to be noted that in the above epoxides there is a complete absence of (a) aryl radicals and (b) radicals in which 5 or more carbon atoms are united in a single uninterrupted single group. R is inherently hydrophile in character as indicated by the fact that it is specified that the precursory diol or polyol HOROH must be water-soluble in substantially all proportions, i. e., water miscible.

Stated another way, what is said previously means that is derived actually or theoretically, or at least derivable, from the diol HOROH, in which the oxygen-linked hydrogen atoms were replaced by Thus, R(OH),,, where n represents a small whole number which is 2 or more, must be Water-soluble. Such limitation excludes polyepoxides if actually derived, or theoretically derived at least, from water-insoluble diols or water-insoluble triols or higher polyols. Suitable polyols may contain as many as 12 to 20 carbon atoms or thereabouts.

Referring to a compound of the type above in the formula H HH HE C in which R is C H (OH), it is obvious that reaction with another mole of epichlorohydrin with appropriate ring closure would produce a triepoxide or, similarly, if R happened to be C H (OH)OC H (OH), one could obtain a tetraepoxide. Actually, such procedure generally yields triepoxides, or mixture with higher epoxides and perhaps in other instances mixture in which diepoxides are also present. Our preference is to use the diepoxides.

There is available commercially at least one diglycidyl ether free from aryl groups and also free from any radical having 5 or more carbon atoms in an uninterrupted chain. This particular diglycidyl ether is obtained by the use of epichlorohydrin in such a manner that ap-- proximately 4 moles of epichlorohydrin yield one mole of the diglycidyl ether, or, stated another way, it can besconsideredas being formed, from one ,mole of;di-, glycerol and 2 moles of, epichlorohydrinso, asrtogive.

the appropriatediepoxide. The molecular weightis approximately 370 and the number of epoxide groups per molecule are approximately 2. For this reason in the first of a series of subsequentexamples this particular diglycidyl ether is used, although obviously any of the others previously described would be just as suitable.

For convenience, this diepoxide will be referred'toas diglycidyl ether A. Such material corresponds in a general way to the previous formula.

Using laboratory procedure we have reacted diethyleneglycol with epichlorohydrin and subsequently with alkali so as to produce a product which, on examination, corresponded approximately to the following compound:

.' The molecular weight of the product was assumed to be 230 and the product was available in laboratory quantities only. For this reason, the subsequent table referring to theuse of this particular diepoxide, which will be referred to as diglycidyl ether B, is in. grams instead of I pounds.

Probably the simplest terminology for these polyepoxides, and particularly diepoxides, to differentiate from comparable aryl compounds, is to use the terminology epoxyalkanes and, more particularly, polyepoxyalkanes orrdiepoxyalkanes. The difiiculty is that the majority of these compounds represent types in which a carbon atom chain is interrupted by an oxygen atom and, thus, they are not strictly alkane derivatives. Furthermore, they may be hydroxylated or represent a heterocyclic ring. The

principal class properly may be referred to as polyepoxypolyglycerols, or diepoxypolyglycerols.

Other examples of diepoxides involving: a heterocyclic ring having, for example, 3 carbon atoms and 2 oxygen PART 2 This part is concerned with the preparation of phenolaldehyde resins of the kind described in detail in U. S. Patent No. 2,499,370, dated March 7, 1950, to De Groote and Keiser, with the following qualifications: said aforementioned patent is limited to resins obtained from difunctional phenols having 4 to 12 carbon atoms in the substituent hydrocarbon radical. For the present purpose the substituent may have as many as 18 carbon atoms, as in the case of resins prepared from tetradecylphenol, substantially para-tetradecylphenol, commercially available. Similarly, resins can be prepared from hexadecylphenol or octadecylphenol. This feature will be referred to subsequently.

In addition to U. S. Patent No. 2,499,370, reference is made also to the following U. S. Patents: Nos. 2,499,365; 2,499,366; and 2,499,367, all dated March 7, 1950, to De Groote and Keiser. These patents, along with the other two previously mentioned patents, describe phenolic resins of the kindherein employed as initial materials.

For practical purposes, the resins having 4 to 12 carbon atoms are most satisfactory, with the additional C 'carbon atom also being very satisfactory. The increased cost-of the C and'C carbon atom phenol renders these raw materials of less importance, at least at the present time.

Patent 2,499,370 describes in detail methods of preparing resinsuseful asintermediates. for preparing the: products .of' the present application, and reference is made illustrated by tetradecylphenol, hexadecylphenol and octadecylphenol; referencetin each instance being to the difunctional phenol, such as the orthoor para-substituted. phenol or a mixture of the same. Such. resins are.de-

scribed also in issued patents, for instance, U. S. Patent No. 2,499,365, dated March 7, 1950, to De Groote and Keiser, such as Example 71a.

It is sometimes desirable to present the resins herein employed in an over-.simplified'form which has appeared.

from time to time in the literature, and particularly in' the patent literature, for instance, it has been stated that the composition is approximated in an idealized form by, the formula- OH OH OH H H1 0 O H H R R n R in the above formula n represents a small whole number varying from 1 to 6, 7, or 8, or more, up to probably 10 or 12 units, particularly when the resin is subjected to heating under a vacuum as described in the literature. A limited sub-genus is in the instance of low molecular weight polymers where the total number of phenol nuclei varies from 3 to 6, i. e., it varies from 1 to 4; R represents an aliphatic hydrocarbonsubstituent, generally an alkyl radical having from 4 to 14 carbon atoms, such as butyl, amyl, hexyl, decyl or dodecyl radical. Where the divalent bridge radical is shown as being derived from formaldehyde, it may, of course, be derived from any other reactive aldehyde having 8 carbon atoms or less.

In the above formula the aldehyde employed in the resin manufacture is formaldehyde. Actually, some other aldehyde such as acetaldehyde, propionaldehyde, or butyraldchyde may be used. The resin unit can be exemplified thus:

resins employed be substantially neutral. In other words,

ifprepared by using a strong acid as a catalyst, such strong acid should be neutralized. Similarly, if a strong base is used as a catalyst it is preferable that the base be neutralized although we have found that sometimes the reaction described proceeded more rapidly in the presence of a small amount of a free base. The amount may be as small as a 200th of a cercent and as much as a few th of a percent. Sometimes moderate increase in caustic soda and caustic potash may be used. However, the-most desirable procedure in practically every case is to have the resin neutral- In preparing resins one .does not get a single polymer,-

11 i. e., one having just 3 units, or just 4 units, or just 5 units, or just 6 units, etc. It is usually a mixture; for instance, one approximating 4 phenolic nuclei will have some trimer and pentamer present. Thus, the molecular weight may be such that it corresponds to a fractional value for n as, for example, 3.5; 4.5; or 5.2.

In the actual manufacture of the resins we found no reason for using other than those which are lowest in price and most readily available commercially. For purposes of convenience suitable resins are characterized in the following table:

Table I Moi. wt. Ex- R' of resin ample R Position derived n molecule number of R om- (based on n+2) Phenyl Para. Formal- 3. 5

dehyde Tertiary butyl do -do 3.5 Secondary butyl. Ortho... 3. 5 882. 5 CyclohexyL... Perm-.. 3. 5 1, 025.5 Tertiary amyl -do. 3. 5 959. 5 Mixed secondary Ortho." 3. 5 805. 5

and tertiary amyl. Propyl Farm... 3. 5 805. 5 Tertiary lloxyl. 3. 5 1, 036. 5 ctyl 3. 5 1, 190. 5 N onyl- 3. 5 1, 267. 5 Decyl... 3. 5 1, 344. 5 Dodecyl-.. 3. 5 1, 498. 5 Tertiary butyl 3. 5 945. 5

Tertiary emyl 3. 5 1,022. 5 r onyl 8. 5 1. 330. 5 Tertiary butyl 3. 5 1,071. 5

Tertiary arnyl -..do ...do 3.5 1,148.5 Nonyl ...do 3. 5 1, 45s. 5 Tertiary butyL. .-.d0.. Propionul- 3. 5 1, 008.5

dehyde. Tertiary amyl 3. 5 1, 085. 5 Nonyl 3. 5 1, 393. 5 Tertiary buty 4. 2 996. 6

Tertiary amyl. 4. 2 1, 083. 4 N l 4. 2 1, 430. 6 4. s 1, 094. 4 4. 8 1, 189. 6 4. 8 1, 570. 4 1. 5 604. 1. 640. 0 1. 5 653.0 1. 5 688. O

PART 3 There have been issued a substantial number of patents which give detailed description of the preparation of oxyalkylated derivatives of resins of the kind previously described. For example, see U. S. Patents 2,499,365; 2,499,366; 2,499,367; 2,499,368; and 2,499,370, all dated March 7, 1950 to De Groote and Keiser.

More specifically, a number of other patents have appeared in which the oxyethylation step is given with considerable detail. See, for example, U. S. Patents 2,581,376; 2,581,377; 2,581,378; 2,581,379; 2,581,380; and 2,581,381, all dated January 8, 1952, to De Groote and Keiser. As to further examples, see U. S. Patent 2,602,052, dated July 1, 1952, to De Groote.

The oxypropylation or, for that matter, the treatment of resins with butylene oxide, glycide, or methyl glycide, has been described in the first of the series in the above mentioned patents, i. e., those issued in 1950.

Reference is made to U. S. Patent 2,557,081, dated June 19, 1951, to De Groote and Keiser. This particular patent describes in considerable detail resins which are first treated with propylene oxide and then with ethylene oxide or with ethylene oxide and then propylene oxide or with both oxides simultaneously.

' In order to avoid an extensive repetition of what is already described in detail in the patent literature, we are referring to the tables beginning in column 21 of U. S. Patent 2,581,376 and extending through column 36. We have simply numbered these products beginning with 1b, allotting, of course, five numbers to each table beginning with the first table. For convenience these sixteen tables are summarized in the following table: 1

Table II 801- Eth- Exam- Phenol Aldehyde vent, Resin, ylene ple No. lbs. lbs. oxide,

lbs.

15 Para-tertiary amyi- Forma1dehyde-- 2b do -.do

.do Para-phenyl. do

Para-phenyl 2. 80 13. b4

Parasecondary 17. 90 3. 50

butyl.

N OTE.F01' ease of comparison, blanks appear in the above table where blanks appear in previously mentioned tables in U. 8. Patent 2,581,376.

, "is Oxy'propylated derivatives -'comparable to -1-bthrough S-Obas described above canreadily be obtained by su'b- 14 description of which appears in detail in said aforehie1itioned U. S. Patent 2,577,081, to De Groote and Keiser.

Table IV 'SeeU; S.Pat. 2,557,081

, 'Ethylene Propylene Flake Ex. No.1. Point Resin used "Resin, oxide, oxide, Weight caustic Ex. No. on lbs. lbs. -lbs. of xylene soda,

in graph ounces above on patent above patent *"Iert. amylphenol formaldehyde; .--.-do 10 eowoocm uzqwcuomoo'uiwmswcnomoomw mama:

stituting a molar equivalent amount of propylene oxide, i. e., 56 lbs. of propylene oxide, for example, for each 44 lbs. of ethylene oxide. We have prepared such a similar series but for sake of brevity only a few will be included for purposes of illustration.

As an illustration of oxypropylated resins involving the use of both ethylene and propylene oxide, a reference is made to the aforementioned U. '8. Patent 2,557,081, dated June 19, 1951, to De Groote and Keiser. The last table in column 2 8 of said patent describes in detail the preparation of a series of oxyalkylated resins in which both propylene and ethylene oxide are employed. Simply by illustration, a series of 27 compounds are included, the

Note the firstseries of 'ninecompounds, 1d through'9d werdprepare'dwith propylene oxide, first and thenethylerie oxide. T he second nine compounds 10d through 1'8'd inclusive, were:=zprepared'using ethylene oxide first arid th'enpropylene oxide, and the last nine compounds, 1 9d through27d, were 'prepared'by random oxyalkylation, i.5.e.; usii1g aJfniXture of the'two'oxides.

In the preparation of the resins, our preference is to use "hydrocarbonesubstitutedi phenols, particularly parasubstituted in which the substituted radical R contains 4'to-18'carbonatoms and particularly 4to -14 carbon atoms. The amount of'alkylene oxide introduced may be comparativelylar'ge in 'eomparison to'fthe initial resin. For-instance, there-may beas much as .50'parts"by weight of' an oxide ormixed oxides 'used for each part by weight of' resin employed.

It will be noted'that the various resins referred to 'in the'aforementioned U. S. Patent 2,499,370are substantially the same type ofmate'rials as referred to in TableI. For--instance,:-resin'-3a of the table is substantially the same as 2a of the patent; re'sin-20a of the table is substantially the same as 34a of'the. patent; and resin 38a of the table-is the'same asr3a of the patent.

In reaction with. polyepoxides,'-arld particularly diepoxides, a large number of'the previously described oxyalkylated re'sins'have been employed. For: convenience, the'following list is sele'ctedindicating the previously-described compounds-and their "molecular weights. Such resins are generally employed as a 50% 'solutionand the polyepoxide employed isa 50% solution, usually both reactants being dissolved in xylene and 'sufiie'ient sodium methylate added to act as-a catalyst, for instance, 1 to2%.- t

Table V Molecular Example number weight PART 4 As previously stated, the final stage reactions involve two moles of an oxyalkylated phenol-aldehyde resin of the kind previously described and one mole of a diglycidyl ether as specified. The reaction is essentially an oxyalkylation reaction and thus may be considered I Y a mechanical standpoint it is a matter of convenience to conduct both classes of reactions in the same equipment. In other words, after the phenolaldehyde resin has been reacted with ethylene oxide, propylene oxide or the like, it is subsequently reacted with a polyepoxide. The polycpoxide reaction can be conducted in an ordinary reaction vessel such as the usual glass laboratory equipment. This is particularly true of the kind used for resin manufacture as described in a number of patents, as for example, U. S. Patent No. 2,499,365. One can use a variety of catalysts in connection with the polyepoxide of the same class employed with monoepoxide. In fact, the reaction will go at an extremely slow rate without any catalyst at all. The usual catalysts include alkaline materials such as caustic soda, caustic potash, sodium methylate, etc. Other catalysts may be acidic in nature and are of the kind characterized by iron and tin chlorides. Furthermore, insoluble catalysts such as clays or specially prepared mineral catalysts have been used. For practical purposes, it is best to use the same catalyst as is used in the initial oxyalkylation step and in many cases there is suificient residual catalyst to serve for the reaction involving the second oxyalkylation step, i. e., the polyepoxide. For this reason, we have preferred to use ,a small amount of finely divided caustic soda or sodium methylate as the initial catalyst and also the catalyst in the second stage. The amount generally employed is 1, 2, or 3% of these alkaline catalysts.

Actually, the reactions of polyepoxides with various resin materials have been thoroughly described in the literature and the procedure is, for all purposes, the same as with glycide which has been described previously.

It goes without saying that the reaction involving the polyepoxide can be conducted in the same manner as the monoepoxide as far as the presence of an inert' solvent to remain.

is concerned, i. e., one that is not oxyalkylation-susceptible. Generally speaking, this is most conveniently an aromatic solvent such as xylene or a higher boiling coal tar solvent, or else a similar high boiling aromatic solvent obtained from petroleum. One can employ an oxygenated solvent such as the diethylether of ethylene glycol, or the diethylether of propylene glycol, or similar ethers, either alone or in combination with a hydrocarbon solvent. The solvent so selected should be one which, of course, is suitable in the oxyalkylation step involving the monoepoxides described subsequently. The solvent selected may depend on the ability to remove it by subsequent distillation if required. Here again it has been our preference to have a solvent present in the oxyalkylation involving the initial stage and permitting the solvent The amount of solvent may be insignificant, depending on whether or not exhaustive oxypropylation is employed. However, since the oxypropylated phenol-aldehyde resins are almost invariably liquids there is no need for the presence of a solvent as when oxyalkylation involves a solid which may be rather high melting. Thus, it is immaterial Whether there is solvent present or not and it is immaterial whether solvent was added in the first stage of oxyalkylation or not, and also it is immaterial whether there was solvent present in the second stage of oxyalkylation or not. The advantage of the presence of solvent is that sometimes it is a convenient way of controlling the reaction temperature and thus in the subsequent examples we have added sufiicient xylene so as to produce a mixture which boils somewhere in the neighborhood of to C. and re moves xylene so as to bring the boiling point of the mixture to about 140 C. during part of the reaction and subsequently removing more xylene so that the mixture refluxed at somewhere between to C. This was purely a convenience and need not be employed unless desired.

Example 10 The oxyalkyated resin employed was the one previously identified as 2b, having a molecular weight of 2169; the amount employed was 217 grams. The resin was dissolved in approximately an equal weight of xylene. The mixture was heated to just short of the boiling point of water, i. e., a little below 100 C. Approximately one half percent of sodium methylate was added, or, more exactly, 1.1 grams. The stirring was continued until there was a solution or distribution of the catalyst. The mixture was heated to a little past 100 C. and left at this temperature while 18.5 grams of the diepoxide (previously identified as A), dissolved in an equal weight of xylene, were added. After the diepoxide was added the temperature was permitted to rise to approximately 109 C. The time required to add the diepoxide was approximately one-half hour. The temperature rose in this period to about 127 C. The temperature rise was controlled by allowing the xylene to reflux over and to separate out the xylene by a phase separating trap. In any event, the temperature was raised shortly to 148l50 C. and allowed to reflux at this temperature for almost three hours. Tests indicated that the reaction was complete at the end of this time; in fact, it probably was complete at a considerably earlier stage. The xylene which had been separated out was returned to the mixture so that the reaction mass at the end of the procedure represented about 50% reaction product and 50% solvent. The procedure employed is, of course, simple in light of what has been said previously; in fact, it corresponds to the usual procedure employed in connection with an oxyalkylating agent such as glycide, i. e., a non-volatile oxyalkylating agent. At the end of the reaction period the mass obtained was a dark, viscous mixture. It could be bleached, of course, by use of charcoal, filtering earths, or the like.

17 Various examples obtained in substantially the same manner as employed are described in the following tables:

18 must weigh the advantage, if any, that the monomer has over other low molal polymers from acost standpoint;

Table VI Ex. Oxyalkyl- Amt., Dlepox- Amt, Catalyst Xylene, Molar Time o Max. No. ed gms. ide used gms. (NaOOHz), gms. ratio reaction, temn, Color and physical state resin grams hrs. C.

217 A 18. 5 1.1 235. 5 2:1 3 150 Dark, viscous mass. 7 450 A 19. 5 2. 3 47s. 5 2:1 4 155 Do. 247 A 18.5 1. 3 255. 5 2:1 3 152 Do. 609 A 18.5 3. 1 627. 5 2:1 5 158 Do. 249 A 18. 5 1. s 267. 5 2:1 3 145 Do. 402 A 18. 5 2. 1 420. 5 2:1 4 150 Do. 708 A 18. 5 3. 6 726. 5 2:1 5 156 Do. 192 A 18. 5 1.0 210. 5 2:1 3 150 Do. 319 A 18. 5 1. 6 337. 5 2:1 3 152 Do. 249 A 1. 9 1. 2 251. 2:1 3 155 Do. 217 B 11.0 1.1 228.0 2:1 3 14s Do. 460 B 11. 0 2. 3 471. 0 2:1 4 150 Do. 247 B 11.0 1. 2 258.0 2:1 3 145 Do. 609 B 11.0 3. 0 620.0 2:1 155 Do. 249 B 11.0 1. 3 260 2:1 5 142 Do. 402 B 11.0 2.0 413 2: 1 4 150 Do. 708 B 11.0 a. 5 719 2: 1 5 155 Do. 192 B 11.0 1. 0 203 2: 1 a 148 Do. 319 B 11.0 1. 6 330 2: 1 3 150 Do. 249 B 1. 1 1. 2 250 2:1 3 150 Do.

Table VII 5 thus, we have found that one might as well attempt to prepareamonomer and fully recognize that there may Probable be present, and probably invariably are present, other Ex N0 gl l gg 332 3 g of low molal polymers in compartively small amounts. used reaction grams Thus, the materials which are most apt to be used for Product practical reasons are either monomers with some small amounts of polymers present or mixtures which have a 3.28 i, substantial amount of polymers present. Indeed, the 51310 51310 21655 mixture can be prepared free from monomers and still g, be sat1sfactor'y. Briefly, then, our preference is to use 8:410 4:200 5: the monomer or the monomer with the minimum amount 14,530 71265 3,632 of higher polymers.

4,210 4, 210 2,100 6,750 6,750 3,375 It has been pointed out PICVIOLISIY'thflt the phenolic 58 itggg 258 nuclei in the epoxide reactant may be directly united, or 0 710 21355 united through a variety of divalent radicals. Actually, it 40 1s ourpreference to use those which are commercially 51200 51205 21600 available and for most practical purposes it means in- E $88 233 stances where the phenolic nucleifare either united di- 41 6 4:050 3 rectly without any intervening linking radical, or else 3 328 g umted by a ketone residue or 1 formaldehyde residue. The commercial blshenols available now in the 0 en PART 5 As will be pointed out subsequently, the preparation of polyepoxides may include the formation of a small amount of material having more than two epoxide groups per molecule. If such compounds are formed they are perfectly suitable except to the extent they may tend to produce ultimate reaction products which are notsolvent-soluble liquids or low-melting solids. Indeed, they tend to form thermosetting resins or insoluble materials. Thus, the specific objective by and large is to produce diepoxides as free as possible from any monoepoxides and as free as possible from polyepoxides in which there are more than two epoxide groups per. molecule. .Thus, for practical purposes what is said hereinafter is largely limited to .polyepoxides in the form of diepoxides.

As has been pointed out previously one of the reactants employed is a diepoxide reactant. It is generallyobtained fromv phenol v:(hydroxybenzene) or substituted phenol. The 'ordinary' or conventional manufactureof the epoxides usually results in the formation of a cogeneric mixture as explained subsequently. Preparation of the monomer or separation of the monomer from the remaining mass of the co-generic mixtureis usually expensive. Ifmonomers were; available commercially (at a low cost, or if they could be prepared without added expense for separation, our preference would, be to use the monomer. Certain monomers. have been prepared and described in the literature and will be referredjto subsequently. However, from a practical standpoint one market illustrate one class. The diphenyl derivatives illustrate a second class, and the materials obtained by reacting substituted monofunctional phenols with an aldehyde illustrate the third class. All the various known classes may be used but our preference rests with these classes due to their availability and ease of preparation,

and also due to the fact that the cost is lower than in other examples.

Although the diepoxide reactants can be produced in more than one way, as pointed out elsewhere, our preference is to produce them by means of the epichlorohydrin reaction referred to indetail subsequently.

One epoxide which can be purchased in the open market and contains only. a. modest amount of polymers corresponds to the deriyativerabbis-phenol A. It can be used as such, or the monomer can be separated by an added step which involves additional expense. This compound of the following structure is preferred as the epoxide reactant and will be used for illustration repeatedly with the full understanding that any of the other epoxides described are equally satisfactory, or that the higher polymers are satisfactory, or that mixtures of the monomer and higher polymers are satisfactory. The formula for this compound is 0 V m CH3 0 Reference has just been made to bis-phenol A and a suitable epoxide derived therefrom. Bis-phenol A is di- 19 hydroxy-diphenyl-dimethyl methane, with the 4,4 isomers predominating and with lesser quantities of the 2,2 and 4,2 isomers being present. It is immaterial which one of these isomers is used and the commercially available mixture is entirely satisfactory,

Attention is again directed to the factthat in the instant part, to wit, Part 5, and in succeeding parts, the text is concerned almost entirely with epoxides in which there is no bridging radical or the bridging radical is derived from an aldehyde or a ketone. It would be immaterial if the divalent linking radical would be derived from the other groups illustrated for the reason that nothing more than mere substitution of. one compound for the other would be required. Thus, what is said hereinafter, although directed to one class or a few classes, applies with equal force and effect to the other classes of epoxide reactants.

If sulfur-containing compounds are prepared they should be freed from impurities with considerable care for the reason that any time that a low-molal sulfurg the use of epichlorohydrin or glycerol dichlorohydrin. A number of problems are involved in attempting to produce these materials free from cogeneric materials of related composition. For a discussion of these difficulties, reference is made to U. S. Patent No. 2,819,212,

beginning at column 7, line 21.

PART 7 Subdivision A The preparations of the diepoxy derivatives of the diphenols, which are sometimes referred to as diglycidyl ethers, have been described in a number of patents. For convenience, reference will be made to two only, to wit, aforementioned U. S. Patent 2,506,486, and aforementioned U. S. Patent No. 2,530,353.

Purely by way of illustration, the following diepoxides, or diglycidyl ethers as they are sometimes termed, are included for purpose of illustration. These particular compounds are described in the two patents just mentioned.

Table VIII Ex- Patent em ple Diphenol Diglycidyl ether refernumber enee Di(epoxypropoxyphenyDmethnne 2, 506, 486 Dl(epoxypropoxyphenyl)methylmethane.-- 2, 506, 486 Di(epoxypropoxyphenyl)dimethylmethane--. 2, 506, 486 Di(epoxypropotyphenyl)ethylmethyl methane. 2, 506, 486 Di(epoxypropoxyphenybdiethylmethane 2, 506, 486 Di(epoxyproporyphenybmethylpropylmethane.-. 2, 506, 486 i(epoxypropoxyphenyl)methylphenylmethane.. 2, 506, 486 Di(epoxypropoxyphenyDethylphenylamethane. 2, 506, 486 Di(epoxypropoxypbenyl)propyl henylmethtme... 2,506, 6 Di(epoxypropoxyphenyl)butylp enylmethane- 2, 506, 486 Di(epoxypropoxyphenyhtolylmethane 2, 506,486 Di(epoxypropoxyphenyl)tolylmethylmethane 2, 506, 486 13A- Dlhydroxy dlpbenyl 4,4'-bis(2,3-epoxypropoxy)diphenyl 2,530,853 14A.-- (CH;)C(C4H5.OH3OH)2 2,2-bis(4e(2,3-epoxypropoxy)2tertlarybuty1phenyDpropane... 2, 530,353

containing compound can react with epichlorohydrin The polyepoxides and particularly the diepoxides can be derived by more than one method as, for example,

Subdivision B As to the preparation of low-molal polymeric epoxides or mixtures reference is made to numerous patents and particularly the aforementioned U. S. Patents Nos. 2,575,- 558 and 2,582,985.

In light of aforementioned U. S. Patent No. 2,575,558,

45 the following examples can be specified by reference to the formula therein provided one still bears in mind it is in essence an over-simplification.

Table IX i t C--C,C ORr[R]fl-R10CCC ORi-[R]n-Ri0-CC-O H: H H1 H: A Hi H H:

(in which the characters have their previous significance) Example R1O- from HR1OH -R- n n Remarks number B1 Hydroxy benzene CH; 1 7 0,1,2 Phenol known as bis-phenol A. Low polymeric mixture about $5 or more where n=0, remainder largely where 6 n=1, some where 7z=2.

32 CH; 1 0,1,2 Phenol knownasbis-phenolB. Seenote 6 regarding B1 above. H

B3 Orthbbiitjrlphenoh'. CH; 1 0,1,2 Even though n is preferably 0, yet the usual reaction product might well contain materials where n is i, or to a 6 lesser degree 2. H BLm-.. Orthoemylphenol CH1 1 0,1,2 Do.

Table Ur -Continued Example R1O from HRIOH R- n 0' Remarks number B5 Orthooctylphenol CH; 1 0, 1,2 Even though n is preferably 0, yet the i uspal reaction product might well coh- C tam materials where n is 1, or to a lesrer negree 2. CH;

B6 Orthononylphenol CH; 1 0,1, 2 Do.

137 Orthododecylphenol CH| 1 0, 1,2 Do.

I CH;

132 Metacrpqnl CH: 1 0,1,2 Se e prior note. This phenol used as mltial material is known as bis-phenol -C- O. For other suitable bis-phenols see (g U. S. Patent 2,564,191.

B9 (1o EH: 1 0, 1, 2 See prior note.

(EH2 6B;

1310 Dibutyl (ortho-para) phenol. 151 1 0,1,2 Do.

B11 Diamyl (ortho-para) phenol. 1g 1 0, 1, 2 Do.

B12 Dioctyl (ortho-para) phenoL g 1 0,1,2 Do.

B13 Dinonyl (ortho-para) phenol. 1% 1 0,1,2 Do.

B14 Diamyl (ortho-para) phenol. 1(5)! 1 0,1,2 Do.

I CH5 B15 do 1g 1 0, 1, 2 Do.

I CzHg B16 Hydroxy benzene (I) 1 0,1,2 Do.

B17 Diomyl phenol (ortho-para)- -S-S 1 0,1, 2 Do.

B18.-. do S- 1 0,1,2 Do.

B19 Dibutyl phenol (ortho-para)- 15 3 1 0,1,2 Do.

B20 d0 .v H H 1 0,1,2 Do.

B21 Dinonylphenol(ortho-para). 3g 1 0,1,2 Do.

B22 Hydroxy benzene E) 1 0,1,2 D0.

B23. 0 o, 1, 2 Do. 7

B24 Ortho-isopropyl phenol 1 0,1,2 See prior note. (As to preparation of 4,4-

isopropylldene *bis-(2-isopropylphonol) see U. S. Patent No. 2,482,748, dated Sept. 27, 1949, to Dietzlor.)

1325...... Para-octyl phenol CH2'S-CHQ 1 0, 1, 2 See prior note. (As to preparation of the phenol sulfide see U. 8. Patent No. 2,488,134, dated Nov. 15, 1949, to Mikeska ei: a1.)

B26 Hydroxybenzone CH3 1 0, 1, 2 See prior note. (As to preparation of the phenol sulfide see U. S. Patent No. (i 2,526,545.)

23 Subdivision C The prior examples have been limited largely to those in which there is no divalent linking radical, as in the case of diphenyl compounds, or where the linking radical is derived from a ketone or aldehyde, particularly a ketone. Needless to say, the same procedure is employed in converting diphenyl into a diglycidyl ether regardless of the nature of the bond between the two phenolic nuclei. For purpose of illustration attention is directed to numerous other diphenols which can be readily converted to a suitable polyepoxide, and particularly diepoxide, reactant.

As previously pointed out the initial phenol may be substituted, and the substituent group in turn may be a cyclic group such as the phenyl group or cyclohexyl group as in the instance of cyclohexylphenol or phenylphenol. Such substituents are usually in the ortho position and may be illustrated by a phenol of the following composition:

Similar phenols which are monofunctional, for instance, paraphenyl phenol or paracyclohexyl phenol with an additional substituent in the ortho position, may be employed in reactions previously referred to, for instance, with formaldehyde or sulfur chlorides to give comparable phenolic compounds having 2 hydroxyls and suitable for subsequent reaction with epichlorohydrin, etc.

Other samples include:

OH OH I Rt ('3 -Rr R2 CH3 C 3 wherein R is a substituent selected from the class consisting of secondary butyl and tertiary butyl groups and R is a substituent selected from the class consisting of alkyl, cycloalkyl, aryl, aralkyl, and alkaryl groups, and wherein said alkyl group contains at least 3 carbon atoms. See U. S. Patent No. 2,515,907.

in which the -C H groups are secondary amyl groups. See U. S. Patent No. 2,504,064.

See U. S. Patent No. 2,503,196.

wherein R is a member of the group consisting of alkyl, and alkoxyalkyl radicals containing from 1 to 5 carbon atoms, inclusive, and aryl and chloraryl radicals of the benzene series. See U. S. Patent No. 2,526,545.

alkyl, cycloalkyl, aryl, aralkyl, and alkaryl groups. See U. S. Patent No. 2,515,906.

CH=CH on 0H See U. S. Patent No. 2,515,908.

As to sulfides, the following compound is of interest:

QSQ

CH OH See U. S. Patent No. 2,331,448.

As to descriptions of various suitable phenol sulfides, reference is made to the following patents: U. S. Patents Nos. 2,246,321, 2,207,719, 2,174,248, 2,139,766, 2,244,021 and 2,195,539.

As' to sulfones, see U. S. Patent No. 2,122,958.

As to suitable compounds obtained by the use of formaldehyde or some other aldehyde, particularly compounds such as out out

Alkyl Alkyl Alkyl Alkyl in which R is a methylene radical, or a substituted methylene radical which represents the residue of an aldehyde and is preferably the unsubstituted methylene radical fides, the disulfides, and the polysulfides. The following formula represents the various dicresol sulfides of this-invention':

OH OH CH3 CH3 in which R and R are alkyl groups, the sum of whose carbon atoms equals 6 to about 20, and R and R each preferably contain 3 to about 10 carbon atoms, and x is 1 to 4. The term sulfides as used in this text, therefore, includes monosulfide, disulfide, and polysulfides.

PART 8 As pointed out previously, the reaction described in Part 4, preceding, resulted in an intermediate which was described thus: (ABA). The reaction described in the instant part has been indicated thus:

Example la The polyepoxide derived intermediate is Example 10, previously described in Table VI. This was obtained by use of a hydrophile polyepoxide. 235.5 grams were employed. This was reacted with 8.5 grams of diepoxide 3A previously described. The amount of xylene was 244 grams. The molal ratio was 2 moles of the polyepoxide derived intermediate to one mole of diepoxide 3A. The catalyst and the solvent and the intermediate were all mixed together and stirred. The diepoxide was then added slowly over a period of minutes. The temperature was raised to 85 C. The reaction took place rapidly and was complete within an hour. Generally speaking, the hydrophile type of polyepoxide seems to react more rapidly than a hydrophobe type and quite often at a considerably lower temperature and a lower reaction time.

The product obtained was a dark viscous mass when the solvent was evaporated.

In-a second series of derivatives hydrophobe diepoxide B1 was employed. This diepoxide has been described previously.

The data are summarized in hereto appended Tables X and XI.

Table XI .Probable Oxalkylmolecular Amount Amount Ex. No. ated resin wt. of of product, of solvent,

used reaction grams grams product PART 9 As to the use of conventional demulsifying agents, reference is made to U. S. Patent No. 2,626,929, dated January 7, 1953, to De Groote, and particularly to Part 3. Everything that appears therein applies with equal force and effect to the instant process, noting only that where reference is made to Example 135 in said text beginning in column 15 and ending in column 18, reference should be to Example 2e, herein described.

PART 10 The products, compounds, or the like herein described can be employed for various purposes and particularly for the resolution of petroleum emulsions of the waterin-oil type as described in detail in Part 5 preceding.

Such products can be reacted with alkylene imines, such as ethylene imine or propylene imine, to produce cationactive materials. Instead of an imine, one may employ what is somewhat equivalent material, to wit, a dialkylaminoepoxypropane of the structure wherein R, and R" are alkyl groups.

It is not necessary to point out that after reaction with a reactant of the kind described which introduces a basic Table X Polyepoxide Catalyst Time of Max. Ex. derived Amt, Diepox- Amt., (N EOOHQ), Xylene, Molar reaction, temp., Color and physical state No. intergms. ide used gms. gms. gms. ratio hrs. C.

mediate product 235. 5 3A 8. 5 2. 4 244 2:1 1 85 Dark viscous mass. 478. 5 3A 8. 5 4. 8 487 2: 1 l D0. 265. 5 3A 8. 5 2.6 274 2:1 1 82 Do. 627. 5 3A 8. 5 6. 3 634 2:1 1 85 D0. 267. 5 3A 8. 5 2. 7 276 2:1 1 80 D0. 420. 0 3A 8. 5 4. 3 429' 2:1 1 86 D0. 726. 5 3A 8. 5 7. 3 735 22 1 1 82 Do. 210. 5 3A 8. 5 2. 2 219 2:1 1 84 D0. 337. 5 3A 8. 5 3. 4 346 2: 1 1 80 D0. 401. 9 3A 1. 7 5.0 504 '221 1 S0 D0. 228.0 B1 13. 8 2. 4 242 2: 1 1 80 D0. 471. 0 131 13.8 4.8 485 221 1 82 D0. 258.0 B1 13. 8 2. 7 272 221 l 80 D0. 620.0 131 13. 8 6. 3 634 2:1 1 84 Do. 260.0 B1 13. 8 2. 7 274 2:1 1 83 D0. 413.0 B1 13. 8 4. 2 427 2:1 1 80 D0. 719.0 B1 13.8 7. 3 733 2:1 1 80 D0. 203.0 B1 13.8 2.1 217 2:1 1' 80 D0. 330.0 B1 13. 8 2. 4 344 211 1 81 Do. 500. 4 B1 2. 8 5:0 505 221 1 80 D0.

2'2 nitrogen atom that the resultant product can be employed for the resolution of emulsions of the water-in-oil type as described in Part 9, preceding, and also for other purposes described hereinafter.

Referring now to the use of the products obtained by reaction with a polyepoxide and certain specified doubly oxyalkylated products obtained in the manner described in Part 8, preceding, it is to be noted that in addition'to their use in the resolution of petroleum emulsions they may be used as emulsifying agents for oils, fats, and waxes, as ingredients in insecticidecompositions, or as detergents and wetting agents in the laundering, scouring, drying, tanning and mordanting industries. They may also be used for preparing boringor metal-cutting oils and cattle dips, as metal pickling inhibitors, and for pharmaceutical purposes.

Not only do these oxyalkylated derivatives have utility as such but they can serve as initial materials for more complicated reactions of the kind ordinarily requiring'a hydroxyl radical. tion, etc.

The oxyalkylated derivatives may be used as valuable additives to lubricating oils, both those derived from petroleum and synthetic lubricating oils. Also, they can be used as additives to hydraulic brake fluids of the aqueous and non-aqueous types. They may be used in connection with other processes where they are injected into an oil or gas well for purpose of removing a mud sheath, increasing the ultimate flow of fluid from the surrounding strata, and particularly in secondary recovery operations using aqueous flood waters. These derivatives also are suitable for use in dry cleaners soaps.

More specifically, such products, depending on the nature of the initial resin, the particular monoepoxide selected, and the ratio of monoepoxide to resin, together with the particular polyepoxide employed, result in a variety of materials which are useful as wetting agents or surface tension reducing agents; as detergents, emulsifiers or dispersing agents; as additives for lubricants, both of the natural petroleum type and the synthetic type, as additives in the flotation of ores, and at times as aids in chemical reactions insofar that demulsification is pro- This includes esterification, ,etheriz'aduced between the insoluble reactants. Furthermore,

such products can be used for a variety of other purposes, including use as corrosive inhibitors, defoamers, asphalt additives, and at times even in the resolution of oil-inwater emulsions. They serve at times as mutual solvents promoting a homogeneous system from two otherwise insoluble phases.

Having thus described our invention What we claim as new and desire to obtain by Letters Patent is:

1. A two-step manufacturing method, the first step involving an intermediate (ABA), which in turn, represents the reaction products of (A) an oxyalkylated phenol-aldehyde resin containing a plurality of active hydrogen atoms, and (B) a non-aryl hydrophile polyepoxide containing at least two 1,2-epoxy rings and having two terminal 1,2-epoxy rings obtained by replacement of an oxygen-linked hydrogen atom in a water-soluble polyhydric alcohol by the radical in which an oxygenlinked hydrogen atom is replaced H H n C-G-OH H said polyepoxides being free from reactive functional groups other than 1,2-epoxy and hydroxyl groupsand characterized by the fact that the divalent linkage uniting the terminal oxirane rings is free from any radical having more than 4 uninterrupted carbon atoms in a single chain; said oxyalkylated phenol-aldehyde resins, reactant (A) being the products derived by oxyalkylation of (aa) an alpha-beta alkylene oxide-having not more than 4;carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide, and (bb) a fusible, organic solvent-soluble, water-insoluble phenol-aldehyde resin; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of tritunctional phenols; said phenol being of the formula in which R is selected from the group consisting of phenyl and saturated hydrocarbon radicals having not more than 24 carbon atoms and substituted in the 2,4,6 position; said oxyalkylated resin being characterized by the introduction into the resin molecule of a plurality of divalent radicals having the formula (R O),," in which R is a member selected from the class consisting of ethylene radicals, propylene radicals, butylene radicals, hydroxypropylene radicals, and hydroxybutylene radicals, and n" is a numeral varying from 1 to 120; with the proviso that the reaction product be a member of the duced for each phenolic nucleus, and that the resin by weight represent at least 2% of the oxyallcylated derivative; the ratio of reactant (A) to reactant (B) being in the proportion of two moles of (A) to one mole of (B); with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of nonthermosetting organic solvent-soluble liquids and solids melting below the point of pyrolysis; with the final proviso that the reactant product be a member of the class of solvent-soluble liquids and solids melting below the point of pyrolysis; and said reaction between (A) and (B) being conducted below the pyrolytic point of the reactants and the resultants of reaction; said second step being the reaction product between 2 moles of the aforementioned intermediate (ABA) and one mole of (C) a phenolic polyepoxide containing at least two 1,2-epoxy rings free from reactive functional groups other than 1,2-epoxy and hydroxyl groups, and cogenerically associated compounds formed in the preparation of said polyepoxides; said epoxides bein monomers and low molal polymers not exceeding the tetramers; said epoxides being selecting from the class consisting of (a) compounds where the phenolic nuclei are directly joined without an intervening bridge radical, and (b) compounds containing a radical in which two phenolic nuclei are joined by a divalent radical selected from the class consisting of ketone residues formed by the elimination of the ketonic oxygen atom, and aldehyde residues obtained by the elimination of the aldehyde oxygen atom, the divalent radical H H C C H H the divalent 0 II C.

radical, the divalent sulfone radical, and the divalent monosulfide radical -S-, the divalent radical -CH SCH and the divalent disulfide radical SS-; said phenolic portion of the diepoxide being obtained from a phenol of the structure class consisting of hydrogen and hydrocarbon substituents,

of the aromatic nucleus, said substituent member having not over 18 carbon atoms; said final product being a member of the class consisting of non-thermosetting organic solvent-soluble liquids and solids melting below the point of pyrolysis; with the final proviso that the reaction product be a member of the class of solvent soluble liquids and solids melting below the point of pyrolysis; and said reaction between (ABA) and (C) being below the pyrolytic point of the reactants and the resultants of reaction.

2. The product obtained by the manufacturing pro cedure defined in claim 1.

3. A two-step manufacturing method, the first step involving an intermediate (ABA) which, in turn, represents the reaction products of (A) an oxyalkylated phenol-aldehyde resin containing a plurality of active hydrogen atoms, and (B) a non-aryl hydrophile polyepoxide containing at least two 1,2-epoxy rings and having two terminal 1,2-epoxy rings obtained by replacement of an oxygen-linked hydrogen atom in a watersoluble polyhydric alcohol by the radical H H H O-CGH H said polyepoxides being free from reactive functional groups other than 1,2-epoxy and hydroxyl groups and characterized by the fact that the divalent linkage uniting the terminal oxirane rings is free from any radical having more than 4 uninterrupted carbon atoms in a single chain; said oxyalkylated phenol-aldehyde resins, reactant (A) being the products derived by oxyalkylation of (aa) an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide, and (bb) a fusible, organic solventsoluble, water-insoluble phenol-aldehyde resin; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is selected from the group consisting of phenyl and saturated hydrocarbon radicals having not more than 24 carbon atoms and substituted in the 2,4,6 position; said oxyalkylated resin being characterized by the introduction into the resin molecule of a plurality of divalent radicals having the formula (R O),,- in which R is a member selected from the class consisting of ethylene radicals, propylene radicals, butylene radicals, hydroxypropylene radicals, and hydroxybutylene radicals, and n is a numeral varying from 1 to with the proviso that at least 2 moles of alkylene oxide be introduced for each phenolic 'nucleus, and that the resin by weight represent at least 2% of the oxyalkylated derivative; the ratio ofreactant (A) to reactant (B) being in the proportion of two moles of (A) to one mole of (B), with the further proviso that said reactive compounds '(A) and (B) be members of the class consisting of nonthermosetting organic solvent-soluble liquids and solids melting below the point of pyrolysis; with the final proviso that the reaction product be a member of the class of solvent-soluble liquids and solids melting below the point of pyrolysis; and said reaction between (A) and (B) being conducted below the pyrolytic point of the reactants and the resultants of reaction; said second step being the reaction product between 2 moles of the aforementioned intermediate (ABA) and one mole of (C) a member of the class consisting of (1) compounds of the following formula and (2) cogenerically associated compounds formed in the preparation of 1) preceding, including monoepoxides; said final product being a member of the class consisting of non-thermosetting organic solvent-soluble liquids and solids melting below the point of pyrolysis; with the final proviso that the reaction product be a. member of the class of solvent-soluble liquids and solids melting below the point of pyrolysis; and said reaction between (ABA) and (C) being conducted below the pyrolytic point of the reactants and the resultants of reaction.

No references cited. 

1. A TWO-STEP MANUFACTURING METHOD, THE FIRST STEP INVOLVING AN INTERMEDIATE (ABA), WHICH IN TURN, REPRESENTS THE REACTION PRODUCTS OF (A) AN OXYALKYLATED PHENOL-ALDEHYDE RESIN CONTAINING A PLURALITY OF ACTIVE HYDROGEN ATOMS, AND (B) A NON-ARYL HYDROPHILE POLYEPOXIDE CONTAINING AT LEAST TWO 1,2-EPOXY RINGS AND HAVING TWO TERMINAL 1,2-EPOXY RINGS OBTAINED BY REPLACEMENT OF AN OXYGEN-LINKED HYDROGEN ATOM IN A WATER-SOLUBLE POLYHYDRIC ALCOHOL BY THE RADICAL IN WHICH AN OXYGENLINKED HYDROGEN ATOM IS REPLACED 